Substituted amino acid amides

ABSTRACT

There are described new amino acid amides of the formula (I) ##STR1## in which n, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , X 1 , X  2  and X 3  having the meaning given in the description, and a process for their preparation. 
     The new amino acid amides of the formula (I) are used as pesticides,

This is continuation of application Ser. No. 08/008,280, filed Jan. 25,1992, now abandoned.

The invention relates to new substituted amino acid amides, to a processfor their preparation, and to their use as pesticides.

It is known that certain substituted amino acid amides such as, forexample, the compound N.sup.α-(t-butyloxycarbonyl)-L-valine-[N-(1-phenylethyl)-amide] or the compoundN.sup.α-(t-butyloxycarbonyl)-L-valine-{N-[1-(2-chlorophenyl)ethyl]-amide} orthe compound N.sup.α-(t-butyloxycarbonyl)-L-valine-{N-methyl-N-[1-(4-chlorophenyl)-ethyl-amide}, have fungicidal properties (cf., for example, EP 398,072).

However, the activity of these previously known compounds is notentirely satisfactory in all fields of application, in particular whenlow amounts and concentrations are applied.

New substituted amino acid amides of the general formula ##STR2## inwhich R¹ represents alkyl, alkenyl, alkinyl, halogenoalkyl,halogenoalkenyl, halogenoalkinyl, cycloalkyl, cycloalkenyl, or in eachcase optionally substituted arylalkyl, aryl, heteroarylalkyl orheteroaryl,

R² represents hydrogen, alkyl or cycloalkyl,

R³ represents hydrogen, alkyl or cycloalkyl and

R⁴ represents alkyl, cycloalkyl, or

R³ and R⁴ together with the carbon atom to which they are bondedrepresent a cycloalkyl ring,

R⁵ represents in each case optionally substituted cycloalkyl,cycloalkenyl, aryl, heterocyclyl, cycloalkylalkyl, cycloalkenyl,arylalkyl or heterocyclylalkyl,

R⁶, R⁷ independent from each other represent hydrogen or in eachoptionally substituted alkyl, alkenyl, alkinyl, cycloalkyl,cycloalkenyl, aryl, hetero-cyclyl, cycloalkylalkyl, cycloalkenylalkyl,arylalkyl, heterocyclylalkyl, or together form a cycloalkylring,

X¹ represents oxygen or sulphur,

X² represents oxygen or sulphur, and

X³ represents oxygen or sulphur,

n represents 0, 1, 2 or 3

but where at least one of the substituents X¹, X² and/or X³ representssulphur.

If appropriate, the compounds of the formula (I) can exist in the formof geometric and/or optical isomers or isomer mixtures of variouscompositions, depending on the nature of the substituents. The inventionclaims the pure isomers as well as the isomer mixtures.

Furthermore, it has been found that the new substituted amino acidamides of the general formula (I) ##STR3## in which n, R¹, R², R⁴, R⁵,R⁶, R⁷, X¹, X², and X³ have the above mentioned meaning,

are obtained when substituted amino acids of the formula (II) ##STR4##in which R¹, R², R³, R⁴ X¹, and X³ have the abovementioned meaning,

are reacted with amines of the formula (III)

    R.sup.2 HN--(CR.sup.7 R.sup.6).sub.n R.sup.5               (III)

in which

n, R², R⁵, R⁶ and R⁷ have the above mentioned meaning,

if appropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary.

Finally, it has been found that the new substituted amino acid amides ofthe general formula (I) have a good activity against pests.

Surprisingly, the substituted amino acid amides of the general formula(I) according to the invention show a considerably better fungicidalactivity than the substituted amino acid amides known from the prior artsuch as, for example, the compound N.sup.α-(t-butyloxycarbonyl)-L-valine-[N-(1-phenylethyl)-amide] or the compoundN.sup.α-(t-butyloxycarbonyl)-L-valine-{N-[1-(2-valine-{N-[1-(2-chlorophenyl)ethyl]-amideor the compound N.sup.α-(t-butyloxycarbonyl)-L-valine-{N-methyl-N-[1-(4-chlorophenyl)ethyl]-amide},which are similar compounds chemically and from the point of view oftheir action.

Formula (I) provides a general definition of the substituted amino acidamides according to the invention. Preferred compounds of the formula(I) are those in which

R¹ represents in each case straight-chain or branched alkyl having 1 to8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 13identical or different halogen atoms, halogenoalkenyl having 2 to 6carbon atoms and 1 to 11 identical or different halogen atoms,halogenoalkinyl having 2 to 6 carbon atoms and 1 to 11 identical ordifferent halogen atoms, cycloalkyl having 3 to 8 carbon atoms,cycloalkenyl having 3 to 8 carbon atoms, or represents arylalkyl, aryl,heteroarylalkyl or heteroaryl, each of which has, if appropriate, 6 to10 carbon atoms in the aryl moiety, or 2 to 9 carbon atoms and 1 to 4identical or different hetero atoms--in particular nitrogen, oxygenand/or sulphur--in the heteroaryl moiety and, if appropriate, 1 to 6carbon atoms in the straight-chain or branched alkyl moiety, and each ofwhich is optionally monosubstituted or polysubstituted in the arylmoiety, or heteroaryl moiety, by identical or different substituents,suitable aryl or heteroaryl substituents in each case being:

halogen, cyano, nitro, hydroxyl, formyl, hydroxycarbonyl, aminocarbonyl,aminosulphonyl, in each case straight-chain or branched alkyl, alkoxy,alkoxyalkyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkoxysulphonyl,alkylsulphonyloxy or dialkylamino, each of which has 1 to 4 carbon atomsin the individual alkyl moieties, in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkylsulphinyl or halogenoalkylsulphonyl, each of which has 1 to4 carbon atoms and 1 to 9 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkylcarbonyloxy,alkoxycarbonyl, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl,alkylcarbonylamino, alkylcarbonylaminoalkyl or alkoximinoalkyl, each ofwhich has 1 to 4 carbon atoms in the individual alkyl moieties, andphenyl, phenoxy, phenylcarbonyl, phenoxycarbonyl or phenylcarbonyloxy,each of which is optionally monosubstituted or polysubstituted in thephenyl moiety by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 4carbon atoms,

R² represents hydrogen, straight-chain or branched alkyl having 1 to 8carbon atoms or cycloalkyl having 3 to 8 carbon atoms,

R³ represents hydrogen, straight-chain or branched alkyl having 1 to 8carbon atoms or cycloalkyl having 3 to 8 carbon atoms and

R⁴ represents straight-chain or branched alkyl having 1 to 8 carbonatoms or cycloalkyl having 3 to 8 carbon atoms, or

R³ and R⁴ together with the carbon atom to which they are bondedrepresent a 3- to 8-membered cycloalkyl ring,

R⁵ represents cycloalkyl, cycloalkylalkyl, cycloalkenylalkyl orcycloalkenyl, each of which has 3 to 8 carbon atoms and each of which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, suitable cycloalkyl or cycloalkenyl substituents in eachcase being: halogen, hydroxyl, in each case straight-chain or branchedalkyl, alkanediyl, alkoxy, alkoxyalkyl, alkylthio or dialkylamino, eachof which has 1 to 6 carbon atoms in the individual alkyl moieties, or ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms,

moreover aryl or arylalkyl having 6 to 10 carbon atoms or heterocyclylor heterocyclylalkyl having 2 to 9 carbon atoms and 1 to 4 identical ordifferent hetero atoms--in particular nitrogen, oxygen and/orsulphur--each of these aryl heterocyclyl radicals optionally beingmonosubstituted or polysubstituted by identical or differentsubstituents, suitable aryl or heterocyclyl substituents in each casebeing those mentioned in the case of R¹,

R⁶, R⁷ independent from each other represent hydrogen, in each casestraight-chain or branched alkyl having 1 to 8 carbon atoms, cyanoalkylhaving 2 to 9 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinylhaving 2 to 8 carbon atoms, or cycloalkyl, cycloalkylalkyl, cycloalkenylor cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in thecycloalkyl or cycloalkenyl moiety and, if appropriate, 1 to 6 carbonatoms in the straight-chain or branched alkyl moiety, and each of whichis optionally monosubstituted or polysubstituted in the cycloalkyl orcycloalkenyl moiety by identical or different substituents, suitablecycloalkyl or cycloalkenyl substituents in each case being:

halogen, hydroxyl, in each case straight-chain or-branched alkyl,alkanediyl, alkoxy, alkoxyalkyl, alkylthio or dialkylamino, each ofwhich has 1 to 6 carbon atoms in the individual alkyl moieties, or ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms,

moreover arylalkyl, aryl, heterocyclylalkyl or heterocyclyl, each ofwhich has, if appropriate, 6 to 10 carbon atoms in the aryl moiety or 2to 9 carbon atoms and 1 to 4 identical or different hetero atoms--inparticular nitrogen, oxygen and/or sulphur--in the heterocyclyl moietyand, where appropriate, 1 to 6 carbon atoms in the straight-chain orbranched alkyl moiety, and each of which is optionally monosubstitutedor polysubstituted in the aryl or heterocyclyl moiety by identical ordifferent substituents, suitable aryl or heterocyclyl substituents ineach case being those mentioned in the case of R¹, or together form acycloalkylring with 1 to 7 carbon atoms,

X¹ represents oxygen or sulphur,

X² represents oxygen or sulphur and

X³ represents oxygen or sulphur,

n represents 0, 1, 2 or 3,

but where at least one of the substituents X¹, X² and/or X³ representssulphur.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents in each case straight-chain or branched alkyl having 1 to6 carbon atoms, alkenyl having 2 to 6 carbon atoms, alkinyl having 2 to6 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms, halogenoalkenyl having 2 to 4carbon atoms and 1 to 7 identical or different halogen atoms,halogenoalkinyl having 2 to 4 carbon atoms and 1 to 7 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms,cycloalkenyl having 3 to 7 carbon atoms, or represents arylalkyl, aryl,heteroarylalkyl or heteroaryl, each of which has, where appropriate, 6to 10 carbon atoms in the aryl moiety, or 2 to 9 carbon atoms and 1 to 3identical or different hereto atoms--in particular nitrogen, oxygenand/or sulphur--in the heteroaryl moiety and, where appropriate, 1 to 4carbon atoms in the straight-chain or branched alkyl moiety, and each ofwhich is optionally monosubstituted to pentasubstituted in the aryl orheteroaryl moiety by identical cal or different substituents, suitablearyl or heteroaryl substituents in each case being:

halogen, cyano, nitro, hydroxyl, formyl, hydroxycarbonyl, aminocarbonyl,aminosulphonyl, in each case straight-chain or branched alkyl, alkoxy,alkoxyalkyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkoxysulphonyl,alkylsulphonyloxy or dialkylamino, each of which has 1 to 4 carbon atomsin the individual alkyl moieties, in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkylsulphinyl or halogenoalkylsulphonyl, each of which has 1 to4 carbon atoms and 1 to 9 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkylcarbonyloxy,alkoxycarbonyl, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl,alkylcarbonylamino, alkylcarbonylaminoalkyl or alkoximinoalkyl, each ofwhich has 1 to 4 carbon atoms in the individual alkyl moieties, andphenyl, phenoxy, phenylcarbonyl, phenoxycarbonyl or phenylcarbonyloxy,each of which is optionally monosubstituted or polysubstituted in thephenyl moiety by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 4carbon atoms,

R² represents hydrogen, straight-chain or branched alkyl having 1 to 6carbon atoms or cycloalkyl having 3 to 7 carbon atoms,

R³ represents hydrogen, straight-chain or branched alkyl having 1 to 6carbon atoms or cycloalkyl having 3 to 7 carbon atoms and

R⁴ represents straight-chain or branched alkyl having 1 to 6 carbonatoms or cycloalkyl having 3 to 6 carbon atoms, or

R³ and R⁴ together with the carbon atom to which they are bondedrepresent a 3- to 7-membered cycloalkyl ring,

R⁵ represents cycloalkyl, cycloalkylalkyl, cycloalkenylalkyl orcycloalkenyl, each of which has 3 to 7 carbon atoms and each of which isoptionally monosubstituted to pentasubstituted by identical or differentsubstituents, suitable cycloalkyl or cycloalkenyl substituents in eachcase being: halogen, hydroxyl, in each case straight-chain or branchedalkyl, alkanediyl, alkoxy, alkoxyalkyl, alkylthio or dialkylamino, eachof which has 1 to 4 carbon atoms in the individual alkyl moieties, or ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms,

moreover represents aryl or arylalkyl having 6 to 10 carbon atom,s orheterocyclyl or heterocyclylalkyl having 2 to 9 carbon atoms and 1 to 3identical or different hereto atoms--in particular nitrogen, oxygenand/or sulphur--each of these aryl or heterocyclyl radicals optionallybeing monosubstituted to pentasubstituted by identical or differentsubstituents, suitable aryl or heterocyclyl substituents in each casebeing those mentioned in the case of R¹,

R⁶, R⁷ independent from each other represents hydrogen, in each casestraight-chain or branched alkyl having 1 to 6 carbon atoms, cyanoalkylhaving 2 to 5 carbon atoms, alkenyl having 1 to 6 carbon atoms, alkinylhaving 2 to 6 carbon atoms, or cycloalkyl, cycloalkylalkyl, cycloalkenylor cycloalkenylalkyl, each of which has 3 to 7 carbon atoms in thecycloalkyl or cycloalkenyl moiety and, where appropriate, 1 to 4 carbonatoms in the straight-chain or branched alkyl moiety, and each of whichis optionally monosubstituted to pentasubstituted in the cycloalkyl or ,cycloalkenyl moiety by identical or different substituents, suitablecycloalkyl or cycloalkenyl substituents in each case being: halogen,hydroxyl, in each case straight-chain or branched alkyl, alkanediyl,alkoxy, alkoxyalkyl, alkylthio or dialkylamino, each of which has 1 to 4carbon atoms in the individual alkyl moieties, or in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, each of which has 1 to 4 carbon atoms and 1 to 9identical or different halogen atoms,

moreover represents arylalkyl, aryl, heterocyclylalkyl or heterocyclyl,each of which has, if appropriate, 6 to 10 carbon atoms in the arylmoiety or 2 to 9 carbon atoms and 1 to 3 identical or different heretoatoms--in particular nitrogen, oxygen and/or sulphur--in theheterocyclyl moiety and, where appropriate, 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety, and each of which is optionallymonosubstituted to pentasubstituted in the aryl or heterocyclyl moietyby identical or different substituents, suitable aryl or heterocyclylsubstituents in each case being those mentioned in the case of R¹, ortogether form a cycloalkylring with 3 to 6 carbon atoms,

n represents 0, 1, 2 or 3,

X¹ represents oxygen or sulphur,

X² represents oxygen or sulphur and

X³ represents oxygen or sulphur,

but where at least one of the substituents X¹, X² and/or X³ representssulphur.

Very particularly preferred compounds of the formula (I) are those inwhich

R¹ represents in each case straight-chain or branched alkyl having 2 to5 carbon atoms, alkenyl having 2 to 4 carbon atoms, alkinyl having 2 to4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkenyl having 2 to 3carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkinyl having 2 to 3 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 6 carbon atoms,cycloalkenyl having 3 to 6 carbon atoms, or represents phenylalkyl orphenyl, each of which has, where appropriate, 1 to 4 carbon atoms in thestraight-chain or branched alkyl moiety, and each of which is optionallymonosubstituted to trisubstituted in the phenyl moiety by identical ordifferent substituents, suitable phenyl substituents in each case being:

halogen, cyano, nitro, hydroxyl, formyl, hydroxycarbonyl, aminocarbonyl,aminosulphonyl, in each case straight-chain or branched alkyl, alkoxy,alkoxyalkyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkoxysulphonyl,alkylsulphonyloxy or dialkylamino, each of which has 1 to 3 carbon atomsin the individual alkyl moieties, in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkylsulphinyl or halogenoalkylsulphonyl, each of which has 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkylcarbonyloxy,alkoxycarbonyl, N-alkylaminocarbonyl, N,N-dialkylaminocarbonyl,alkylcarbonylamino, alkylcarbonylaminoalkyl or alkoximinoalkyl, each ofwhich has 1 to 3 carbon atoms in the individual alkyl moieties, andphenyl, phenoxy, phenylcarbonyl, phenoxycarbonyl or phenylcarbonyloxy,each of which is optionally monosubstituted or polysubstituted in thephenyl moiety by identical or different substituents from the seriescomprising halogen and/or straight-chain or branched alkyl having 1 to 3carbon atoms,

R² represents hydrogen, straight-chain or branched alkyl having 1 to 4carbon atoms or cycloalkyl having 3 to 6 carbon atoms,

R³ represents hydrogen, straight-chain or branchedalkyl having 1 to 4carbon atoms or cycloalkyl having 3 to 6 carbon atoms and

R⁴ represents straight-chain or branched alkyl having 1 to 4 carbonatoms or cycloalkyl having 3 to 6 carbon atoms, or

R³ and R⁴ together with the carbon atom to which they are bondedrepresent a 3- to 6-membered cycloalkyl ring,

R⁵ represents cycloalkyl, cycloalkylalkyl, cycloalkenylalkyl orcycloalkenyl, each of which has 3 to 6 carbon atoms and each of which isoptionally monosubstituted to trisubstituted by identical or differentsubstituents, suitable cycloalkyl or cycloalkenyl substituents in eachcase being:

halogen, hydroxyl, in each case straight-chain or branched alkyl,alkanediyl, alkoxy, alkoxyalkyl, alkylthio or dialkylamino, each ofwhich has 1 to 3 carbon atoms in the individual alkyl moieties, or ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halegenoalkylthio, each of which has 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms,

moreover represents phenyl or phenylalkyl or heterocyclyl orheterocyclylalkyl having 2 to 9 carbon atoms and 1 to 3 identical ordifferent hereto atoms--in particular nitrogen, oxygen and/orsulphur--each of these phenyl or heterocyclyl radicals optionally beingmonosubstituted to trisubstituted by identical or differentsubstituents, suitable phenyl or heterocyclyl substituents in each casebeing those mentioned in the case of R¹,

R⁶, R⁷ independent from each other represents hydrogen, in each casestraight-chain or branched alkyl having 1 to 4 carbon atoms, cyanoalkylhaving 2 to 3 carbon atoms, alkenyl having 2 to 4 carbon atoms, alkinylhaving 2 to 4 carbon atoms, orcycloalkyl, cycloalkylalkyl, cycloalkenylor cycloalkenylalkyl, each of which has 3 to 6 carbon atoms in thecycloalkyl or cycloalkenyl moiety and, where appropriate, 1 to 3 carbonatoms in the straight-chain or branched alkyl moiety, and each of whichis optionally monosubstituted to trisubstituted in the cycloalkyl orcycloalkenyl moiety by identical or different substituents, suitablecycloalkyl or cycloalkenyl substituents in each case being:

halogen, hydroxyl, in each case straight-chain or branched alkyl,alkanediyl, alkoxy, alkoxyalkyl, alkylthio or dialkylamino, each ofwhich has to 3 carbon atoms in the individual alkyl moieties, or in eachcase straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, each of which has 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms,

moreover represents phenylalkyl, phenyl, heterocyclylalkyl orheterocyclyl, each of which has, where appropriate, 2 to 9 carbon atomsand 1 to 3 identical or different hetero atoms--in particular-nitrogen,oxygen and/or sulphur--in the heterocyclyl moiety and, whereappropriate, 1 to 3 carbon atoms in the straight-chain or branched alkylmoiety, and each of which is optionally monosubstituted totrisubstituted in the phenyl or heterocyclyl moiety by identical ordifferent substituents, suitable aryl or heterocyclyl substituents ineach case being those mentioned in the case of R¹, or together form acycloaklylring with 3 to 5 carbon atoms

X¹ represents oxygen or sulphur,

X² represents oxygen or sulphur and

X³ represents oxygen or sulphur,

n represents 1 or 2,

but where at least one of the substituents X¹, X² and/or X³ representssulphur.

Reference must be made to the compounds mentioned individually in thepreparation examples.

If, for example, N.sup.α -(i-propylthio-carbonyl)-L-valine andα-(4-methylphenyl)-ethylamine are used as starting substances, thecourse of the reaction of the process according to the invention can berepresented by the following equation: ##STR5##

Formula (II) provides a general definition of the substituted aminoacids required as starting substances for carrying out the processaccording to the invention. In this formula (II), R¹, R², R³, R⁴, X¹, X²and X³ preferably represent those radicals which have already beenmentioned in connection with the description of the substances of theformula (I) according to the invention as being preferred for thesesubstituents. The substituted amino acids of the formula (II) are knownor can be prepared analogously to known processes (cf., for example,Houben-Weyl "Methoden der organischen Chemie" [Methods in OrganicChemistry] Volume 15/1, 4th Edition, Thieme Verlag Stuttgart 1977; JP53148530; JP 52151146; J. Org. Chem. 43, 2930-2932 [1978]; J. Chem.Soc., Perkin Trans. 1, 1972, 1983-1985; Chem. Ber. 104, 3156-3167[1971]; J. Org. Chem. 36, 49-59 [1971]; Helv. Chim. Acta 52, 282-291[1969]; Tetrahedron 34, 2763-2766 [1978]; Chem. Pharm. Bull. 19, 912-929[1971]; J. Chem. Soc. 1952, 2076-2079).

Formula (III) provides a general definition of the amines required asstarting substances for carrying out the process according to theinvention. In this formula (III), R⁵ and R⁶ preferably represent thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for these substituents.

The amines of the formula (III) are generally known compounds of organicchemistry or can be obtained analogously to generally known processes.

Suitable diluents for carrying out the process according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as, for example, benzine, benzene, toluene, xylene, chlorobenzene,dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,chloroform or carbon tetrachloride; ethers such as diethyl ether,diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethylether or ethylene glycol diethyl ether; ketones such as acetone orbutanone or methyl isobutyl ketone; nitriles .such as acetonitrile,propionitrile or benzonitrile; amides such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide, esters such as methyl acetate or ethylacetate, or sulphoxides such as dimethyl sulphoxide.

If appropriate, the process according to the invention is carried out inthe presence of a suitable condensing agent. Suitable condensing agentsare all those which can customarily be used for such amidationreactions. Examples which may be mentioned are acid halide formers suchas phosphorus tribromide, phosphorus pentachloride, phosphorusoxychloride or thionyl chloride, anhydride formers such as ethylchloroformate, isobutyl chloroformate or methanesulphonyl chloride,carbodiimides such as N,N'-dicyclohexylcarbodiimide (DCC) or othercustomary condensing agents such as N,N'-carbonyldiimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) ortriphenylphosphine/carbon tetrachloride.

The process according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable reaction auxiliariesare all inorganic and organic bases which can customarily be used. Thehydrides, hydroxide, amides, alcoholates, carbonates or hydrogencarbonates of alkali metals are preferably used such as, for example,sodium hydride, sodium amide, sodium hydroxide, sodium methylate, sodiumethylate, potassium t-butylate, sodium carbonate or sodium hydrogencarbonate, or else tertiary amines such as, for example, triethylamine,N-methylpiperidine, N,N-dimethylaniline, pyridine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -60° C. and 220° C.,preferably at temperatures between -20° C. and 100° C.

To carry out the process according to the invention, 1.0 to 10.0 moles,preferably 1.0 to 2.0 moles, of amine of the formula (III) and, ifappropriate--1.0 to 3.0 moles, preferably 1.0 to 2.0 moles, ofcondensing agent or reaction auxiliary are generally employed per moleof substituted amino acid of the formula (II). The reaction is carriedout and the reaction products are worked up and isolated by generallycustomary methods (cf., in this context, for example Houben Weyl"Methoden der organischen Chemie" [Methods in Organic Chemistry], Volume15/2, 4th Edition, Thieme Verlag Stuttgart 1977 or the PreparationExamples). The end products of the formula (I) are purified with the aidof customary processes, for example by column chromatography or byrecrystallisation.

They are characterised with the aid of the melting point or, in the caseof non-crystallising compounds, with the aid of proton nuclear resonancespectroscopy (¹ H NMR).

The active compounds according to the invention have a powerful actionagainst pests and can be employed in practice for combating undesiredharmful organisms. The active compounds are suitable for use as plantprotection agents, in particular as fungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Pythium species, such as, for example, Pythium ultimum; Phytophthoraspecies, such as, for example, Phythophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries; Ustilagospecies, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea; Septoriaspecies, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

In this context, the active compounds according to the invention can beemployed with particularly good success for combating diseases .in fruitand vegetable growing such as, for example, against the causative oftomato rot (Phytophthora inf estans).

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV cold mist and warm mistformulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methylethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present is theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and in mixtureswith fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation the active compound itself into the soil. The seed of theplants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%. In the treatment of seed, amounts of active compound of 0.001 to50 g per kilogram of seed, preferably 0.01 to 10 g, are generallyrequired.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES EXAMPLE 1 ##STR6##

To 3.28 g (0.015 mol) of N.sup.α -(i-propylthio-carbonyl)-L-valine in 50ml of dichloromethane there are added, at -20° C. 1.5 g (0 015 mol) ofN-methylpiperidine and subsequently dropwise and with stirring at -20°C. 2.0 g (0.015 mol) of isobutyl chloroformate and, after the additionhas ended, the mixture is stirred for a further 10 minutes at -20° C.and then cooled to -60° C. and 2.0 g (0.015 mol) ofα-(4-methylphenyl)-ethylamine are added, during which process thetemperature should not rise above -15° C. The mixture is subsequentlystirred for a further 2 hours at. -15° C. and 15 hours at roomtemperature, solid which has precipitated is then filtered off andwashed with dichloromethane, the filtrate is concentrated in vacuo, theresidue is taken up in water, the mixture is extracted several timesusing ethyl acetate, and the combined ethyl acetate phases are washedwith aqueous sodium hydrogen carbonate solution and water and dried oversodium sulphate, and the solvent is removed in vacuo.

2.8 g (58% of theory) of N.sup.α -(i-propylthio-carbonyl)-L-valine-[N-(4-methylphenyl)-ethylamide] ofmelting point 168° C. are obtained.

Preparation of the starting compound: ##STR7##

To 37.5 g (0.32 mol) of L-valine and 88.0 g (0.64 mol) of potassiumcarbonate in 400 ml of water there are added dropwise with stirring andice-cooling 45 g (0.32 mol) of isopropyl chlorothioformate and, when theaddition has ended, the mixture is stirred for a further hour at 0° C.,acidified with concentrated hydrochloric acid and extracted three timesusing 200 ml portions of toluene, and the combined organic phases aredried over sodium sulphate, and the solvent is removed in vacuo. Theviscous oil which remains crystallises after some time. 37.2 g (53% oftheory) of N.sup.α -(i-propylthio-carbonyl)-L-valine of melting point65° C. are obtained.

The following substituted amino acid amides of the general formula (I)are obtained analogously and following the general preparationinstructions:

    __________________________________________________________________________     ##STR8##                                (I)                                  Ex. No.                                                                            R.sup.1                                                                           R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                           R.sup.5                                                                          R.sup.6    X.sup.1                                                                         X.sup.2                                                                         X.sup.3                                                                         m.p./°C.*)                        __________________________________________________________________________    2    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR9##  S O O 189 (rac.)                               3    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR10## S O O 170 (rac.)                               4    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR11## S O O 148 (rac.)                               5    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                         C.sub.6 H.sub.5                                                                          S O O 179                                      6    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR12## S O O 191 (R+)                                 7    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                         C.sub.6 H.sub.5                                                                          S O O 199 (R+)                                 8    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                         C.sub.6 H.sub.5                                                                          S O O 176 (rac.)                               9    i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR13## S O O 196 (rac.)                               10   i-C.sub.3 H.sub.7                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR14## S O O 204 (rac.)                               11   t-C.sub.4 H.sub.9                                                                 H H i-C.sub.3 H.sub.7                                                                 CH.sub.3                                                                          ##STR15## S O O 179 (rac.)                               __________________________________________________________________________     *)The stereochemical data in each case relate to the amine component in       the amide moiety. Exclusively Lamino acid derivatives were employed as        starting compounds of the formula (II).                                  

Use Example

In the use example which follows, the compound listed below wereemployed as comparison substance: ##STR16##

N.sup.α-(t-butyloxycarbonyl)-L-valine-{N-methyl-N-[1-(4-chlorophenyl)-ethyl]-amide}##STR17##

N.sup.α -(t-butyloxcarbonyl)-L-valine-[N-(1-phenylethyl)-amide]##STR18##

N.sup.α-(t-butyloxycarbonyl)-L-valine-{N-[1-(2-chlorophenyl)ethyl]-amide}

(disclosed in EP 398,072)

Example A

Phytophthora test (tomato)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, one part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Phytophthora infestans.

The plants are then placed in an incubation cabinet at 20° C. underrelative atmospheric humidity of approx. 100%.

The evaluation is effected 3 days after inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds of the Preparation Example 1, 2, 3,4, 5, 7, 10 and 11 and which show a degree of activity of up to 100% atan active compound concentration of 100 ppm.

We claim:
 1. An amino acid amine of the formula ##STR19## in which R¹represents alkyl having 2 to 5 carbon atoms,R² represents hydrogen,alkyl or cycloalkyl, R³ represents alkyl having 1 to 6 carbon atoms, R⁴represents hydrogen, R⁵ represents phenyl optionally substituted by atleast one member selected from the group consisting of fluorine,chlorine, or alkyl or alkoxy having 1 to 3 carbon atoms, R⁶ representshydrogen, R⁷ represents alkyl having 1 to 4 carbon atoms, X¹ representssulphur, X² represents oxygen, X³ represents oxygen, and n represents 1,2 or
 3. 2. A compound according to claim 1, in which n represents
 1. 3.A compound according to claim 2, in whichR¹ represents isopropyl, R³represents isopropyl, R⁵ represents phenyl optionally substituted by atleast one member selected from the group consisting of fluorine,chlorine, Methyl, ethyl or methoxy, and R⁷ represents methyl.
 4. Afungicidal composition comprising a fungicidally effective amount of acompound according to claim 1 and a diluent.
 5. A method of combattingfungi which comprises applying to such fungi or to a fungus habitat afungicidally effective amount of a compound according to claim
 1. 6. Acompound selected from the group consisting of: ##STR20##
 7. Thecompound according to claim 6, wherein such compound is N.sup.α-(i-propylthio-carbonyl)-L-valine-[N-(4-methylphenyl)ethylamide] of theformula ##STR21##
 8. A compound according to claim 6, wherein suchcompound is ##STR22##
 9. A compound according to claim 6, wherein suchcompound is ##STR23##
 10. A compound according to claim 6, wherein suchcompound is ##STR24##
 11. A compound according to claim 6, wherein suchcompound is ##STR25##
 12. A compound according to claim 6, wherein suchcompound is ##STR26##
 13. A compound according to claim 6, wherein suchcompound is ##STR27##
 14. A fungicidal composition comprising afungicidally effective amount of a compound according to claim 6, and adiluent.
 15. A method of combatting fungi which comprises applying tosuch fungi or to a fungus habitat a fungicidally effective amount of acompound according to claim 6.